EP3107879B1 - Fils supraconducteurs et procédés pour les produire - Google Patents

Fils supraconducteurs et procédés pour les produire Download PDF

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EP3107879B1
EP3107879B1 EP15792961.3A EP15792961A EP3107879B1 EP 3107879 B1 EP3107879 B1 EP 3107879B1 EP 15792961 A EP15792961 A EP 15792961A EP 3107879 B1 EP3107879 B1 EP 3107879B1
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Prior art keywords
alloy
layer
superconducting
metal oxide
disposed around
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EP3107879A4 (fr
EP3107879A2 (fr
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Xingchen XU
Michael D. SUMPTION
Xuan PENG
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Hyper Tech Research Inc
Ohio State University
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Hyper Tech Research Inc
Ohio State University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B12/00—Superconductive or hyperconductive conductors, cables, or transmission lines
    • H01B12/02—Superconductive or hyperconductive conductors, cables, or transmission lines characterised by their form
    • H01B12/10—Multi-filaments embedded in normal conductors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F5/12—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of wires
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
    • B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11C—STATIC STORES
    • G11C16/00—Erasable programmable read-only memories
    • G11C16/02—Erasable programmable read-only memories electrically programmable
    • G11C16/06—Auxiliary circuits, e.g. for writing into memory
    • G11C16/26—Sensing or reading circuits; Data output circuits
    • G11C16/28—Sensing or reading circuits; Data output circuits using differential sensing or reference cells, e.g. dummy cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F6/00—Superconducting magnets; Superconducting coils
    • H01F6/06—Coils, e.g. winding, insulating, terminating or casing arrangements therefor
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00—Superconducting devices
    • H10N60/01—Manufacture or treatment
    • H10N60/0184—Manufacture or treatment of devices comprising intermetallic compounds of type A-15, e.g. Nb3Sn
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00—Superconducting devices
    • H10N60/20—Permanent superconducting devices
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0031—Matrix based on refractory metals, W, Mo, Nb, Hf, Ta, Zr, Ti, V or alloys thereof

Definitions

  • Superconductivity is a phenomenon occurring in certain materials below certain temperatures, characterized by zero electrical resistance and expulsion of magnetic fields.
  • Superconducting magnets are some of the most powerful electromagnets, and can be used in magnetic resonance imaging (MRI) machines, nuclear magnetic resonance (NMR) spectrometers, mass spectrometers, particle accelerators, and in plasma confinement in fusion reactors.
  • MRI magnetic resonance imaging
  • NMR nuclear magnetic resonance
  • superconducting wires comprising filaments formed from niobium-based superconductors, such as niobium tin (Nb 3 Sn), have attracted interest for use in a variety of electromagnetic applications, such as magnets (e.g., high-field (10-20 T) magnets), motors, and transformers.
  • US 2006/0081307 shows a superconducting wire comprising a matrix comprising a Cu-based metal an subelements embedded in the matrix. These subelements comprise a non-superconducting core and superconducting (Nb 3 Sn) layer and a barrier layer coaxially disposed around the superconducting layer.
  • Nb 3 Sn non-superconducting core and superconducting
  • barrier layer coaxially disposed around the superconducting layer.
  • the superconducting wires can comprise a metallic matrix (for example, a Cu-based metal) and at least one continuous subelement embedded in the matrix.
  • Each subelement can comprise a non-superconducting core, a superconducting layer coaxially disposed around the non-superconducting core, and a barrier layer coaxially disposed around the superconducting layer.
  • the superconducting layer can comprise a plurality of Nb 3 Sn grains stabilized by metal oxide particulates disposed therein.
  • the Nb 3 Sn grains can have an average grain size of from 5 nm to 90 nm (for example from 15 nm to 50 nm).
  • the diameter of each subelement can be from 5 ⁇ m to 150 ⁇ m.
  • the superconducting layer can, in some examples, further comprise a dopant, for example, to improve the superconducting properties of the superconducting layer.
  • a dopant for example, to improve the superconducting properties of the superconducting layer.
  • suitable dopants include, but are not limited to, Ti, Ta, and combinations thereof.
  • the barrier layer can comprise a Nb alloy, a Ta alloy, a Ti alloy, or a combination thereof. In certain cases, the barrier layer comprises a Nb alloy. In some examples, the Nb alloy can comprise an alloy formed from Nb and a metal that has an oxidation potential greater than the oxidation potential of Nb. In some examples, the Nb alloy is selected from the group consisting of a Nb-Zr alloy, a Nb-Al alloy, a Nb-Ti alloy, and combinations thereof.
  • the metal oxide particulates disposed in the superconducting layer can comprise a metal that has an oxidation potential greater than the oxidation potential of Nb.
  • the metal oxide particulates can comprise a metal oxide selected from the group consisting of ZrO 2 , Al 2 O 3 , TiO 2 , and combinations thereof.
  • superconducting wire precursors can be heat treated to prepare superconducting wires, such as those described herein.
  • the superconducting wire precursor can comprise a metallic matrix of Cu-based metal and at least one continuous subelement precursor embedded in the matrix.
  • Each subelement precursor can comprise, in some examples:
  • the method may include heat treating the superconducting wire precursor of claim 13 to form a superconducting wire comprising a superconducting phase comprising Nb 3 Sn.
  • the method may also include heat treating the superconducting wire precursor comprises heating the superconducting wire precursor at a temperature of at least 600°C , heating the superconducting wire precursor for at least 10 minutes, or a combination thereof
  • 'layers' of particular composition within the superconducting wires and superconducting wire precursors described herein. It should be noted that 'layers' formed from a particular material (e.g., a particular alloy) can be formed from an integral piece of the particular material (e.g., the particular alloy), or from a plurality of pieces of the particular material (e.g., the particular alloy) that together combine to form the layer.
  • a particular material e.g., a particular alloy
  • the superconducting wires can comprise a metallic matrix and at least one continuous subelement (also referred to as a filament) embedded in the matrix.
  • the metallic matrix can comprise any suitable metal or combination of metals.
  • the metallic matrix can be formed from a metal or combination of metals that is electrically conductive at temperatures below 77 K.
  • the metal or combination of metals forming the metallic matrix can exhibit a coefficient of thermal expansion that is substantially the same or greater than the coefficient of thermal expansion of Nb 3 Sn.
  • the metallic matrix can comprise a Cu-based metal (e.g., copper or an alloy thereof).
  • the superconducting wires can include any number of subelements, as known in the art, to prepare a suitable superconducting wire for a particular application.
  • the superconducting wire can comprise a single subelement.
  • the superconducting wire can comprise a plurality of subelements.
  • the superconducting wire can comprise from 1 to 25,000 subelements (e.g., from 1 to 61 filaments, from 1 to 244 filaments, from 1 to 366 filaments, from 1 to 1,000 filaments, from 1 to 2,500 filaments, from 1 to 5,000 filaments, from 1 to 15,000 filaments, or from 10,000 to 25,000 filaments).
  • Each subelement can comprise a non-superconducting core, a superconducting layer coaxially disposed around the non-superconducting core, and a barrier layer coaxially disposed around the superconducting layer.
  • the non-superconducting core can comprise any suitable non-superconducting material.
  • the non-superconducting core can comprise a Sn-based metal (e.g., Sn metal or an alloy thereof).
  • the non-superconducting core can comprise a Sn-Cu alloy.
  • the non-superconducting core can comprise a hollow core.
  • the superconducting layer coaxially disposed around the non-superconducting core can comprise a Nb-based superconductor, such as Nb 3 Sn.
  • the superconducting layer can comprise a plurality of Nb 3 Sn grains stabilized by metal oxide particulates disposed therein (e.g., dispersed throughout the superconducting layer).
  • the Nb 3 Sn grains can have a fine grained microstructure (e.g., an average grain size of from 5 nm to 90 nm).
  • the metal oxide particulates can serve to stabilize the fine grained microstructure of the Nb 3 Sn at elevated temperatures at which the Nb 3 Sn is formed (e.g., from 600°C to 850°C) and inhibit Nb 3 Sn grain growth, thus allowing Nb 3 Sn to maintain its fine grained microstructure when heat treated.
  • the average grain size of the plurality of Nb 3 Sn grains in the superconducting layer can be determined using standard methods known in the art, such scanning electron microscopy (SEM).
  • the plurality of Nb 3 Sn grains can have an average grain size of 5 nm or more (e.g., 10 nm or more, 15 nm or more, 20 nm or more, 25 nm or more, 30 nm or more, 35 nm or more, 40 nm or more, 45 nm or more, 50 nm or more, 55 nm or more, 60 nm or more, 65 nm or more, 70 nm or more, 75 nm or more, 80 nm or more, or 85 nm or more).
  • the plurality of Nb 3 Sn grains can have an average grain size of 90 nm or less (e.g., 85 nm or less, 80 nm or less, 75 nm or less, 70 nm or less, 65 nm or less, 60 nm or less, 55 nm or less, 50 nm or less, 45 nm or less, 40 nm or less, 35 nm or less, 30 nm or less, 25 nm or less, 20 nm or less, 15 nm or less, or 10 nm or less).
  • 90 nm or less e.g., 85 nm or less, 80 nm or less, 75 nm or less, 70 nm or less, 65 nm or less, 60 nm or less, 55 nm or less, 50 nm or less, 45 nm or less, 40 nm or less, 35 nm or less, 30 nm or less, 25 nm or less, 20 nm or less,
  • the average grain size of the plurality of Nb 3 Sn grains can range from any of the minimum values described above to any of the maximum values described above, for example from 5 nm to 90 nm (e.g., from 15 nm to 90 nm, from 5 nm to 50 nm, from 15 nm to 50 nm, from 50 nm to 90 nm, from 5 nm to 30 nm, from 15 nm to 30 nm, from 5 nm to 45 nm, from 15 nm to 45 nm, from 30 nm to 45 nm, from 45 nm to 60 nm, from 60 nm, to 75 nm, or from 75 nm to 90 nm).
  • 5 nm to 90 nm e.g., from 15 nm to 90 nm, from 5 nm to 50 nm, from 15 nm to 50 nm, from 50 nm to 90 nm, from 5 nm to 30
  • the superconducting layer can further comprise a dopant.
  • Dopants can be incorporated into the superconducting layer to improve the superconducting properties of the superconducting layer. Suitable dopants are known in the art, and include, for example, Ti, Ta, and combinations thereof.
  • the metal oxide particulates disposed in the superconducting layer can comprise a metal that has an oxidation potential greater than the oxidation potential of Nb.
  • the metal oxide particulates disposed in the superconducting layer can comprise a metal that is less noble than Nb (e.g., a metal that appears lower than Nb in a galvanic series).
  • the metal oxide particulates can comprise a metal oxide selected from the group consisting of ZrO 2 , Al 2 O 3 , TiO 2 , and combinations thereof.
  • the superconducting layer can be substantially free of ZrO 2 particulates.
  • the barrier layer can comprise any suitable material that can inhibit diffusion of the superconducting layer into the metallic matrix.
  • the barrier layer can comprise Nb metal or an alloy thereof, Ta metal or an alloy thereof, Ti metal or an alloy thereof, Mo metal or an alloy thereof, or a combination thereof.
  • the barrier layer can comprise Nb metal or an alloy thereof.
  • the barrier layer can comprise a Nb alloy.
  • the Nb alloy can comprise an alloy formed from Nb and a metal that has an oxidation potential greater than the oxidation potential of Nb.
  • the Nb alloy can comprise an alloy formed from Nb and a metal that is less noble than Nb (e.g., a metal that appears lower than Nb in a galvanic series).
  • suitable Nb alloys include, but are not limited to, Nb-Zr alloys, Nb-Al alloys, Nb-Ti alloys, Nb-Ta alloys, Nb-Be alloys, Nb-Ni alloys, Nb-Fe alloys, Nb-Sn alloys, and combinations thereof.
  • the Nb alloy can be selected from the group consisting of a Nb-Zr alloy, a Nb-Al alloy, a Nb-Ti alloy, and combinations thereof.
  • the superconducting layer (e.g., the Nb 3 Sn phase) can exhibit improved properties (e.g., an improved high-field critical current density ( J c )) relative to existing niobium-tin superconductors.
  • the superconducting wire comprising the superconducting layer can therefore also exhibit improved properties relative to existing niobium-tin superconducting wires.
  • the superconducting layer (e.g., the Nb 3 Sn layer) can have a high-field critical current density of 5,000 A/mm 2 or more (e.g., 5,500 A/mm 2 or more; 6,000 A/mm 2 or more; 6,500 A/mm 2 or more; 7,000 A/mm 2 or more; 7,500 A/mm 2 or more; 8,000 A/mm 2 or more; 8,500 A/mm 2 or more; 9,000 A/mm 2 or more; 9,500 A/mm 2 or more; 10,000 A/mm 2 or more; 11,000 A/mm 2 or more; 12,000 A/mm 2 or more; 13,000 A/mm 2 or more; 14,000 A/mm 2 or more; 15,000 A/mm 2 or more; 16,000 A/mm 2 or more; 17,000 A/mm 2 or more; 18,000 A/mm 2 or more; 19,000 A/mm 2 or more; or 20,000 A/mm 2 or more) at a temperature of 4.2 K in a magnetic field of 12 T.
  • 5,000 A/mm 2 or more e
  • the superconducting layer (e.g., the Nb 3 Sn layer) can have a critical current density of 21,000 A/mm 2 or less (e.g., 20,000 A/mm 2 or less; 19,000 A/mm 2 or less; 18,000 A/mm 2 or less; 17,000 A/mm 2 or less; 16,000 A/mm 2 or less; 15,000 A/mm 2 or less; 14,000 A/mm 2 or less; 13,000 A/mm 2 or less; 12,000 A/mm 2 or less; 11,000 A/mm 2 or less; 10,000 A/mm 2 or less; 9,500 A/mm 2 or less; 9,000 A/mm 2 or less; 8,500 A/mm 2 or less; 8,000 A/mm 2 or less; 7,500 A/mm 2 or less; 7,000 A/mm 2 or less; 6,500 A/mm 2 or less; 6,000 A/mm 2 or less; or 5,500 A/mm 2 or less) at a temperature of 4.2 K in a magnetic field of 12 T.
  • a critical current density e.g., 20,000
  • the superconducting layer can have a high-field critical current density at a temperature of 4.2 K in a magnetic field of 12 T ranging from any of the minimum values described above to any of the maximum values described above.
  • the superconducting layer e.g., the Nb 3 Sn layer
  • the flux pinning force vs. field ( F p -B ) curve of the superconducting layer can peak at 0.2 times the irreversibility field ( B irr ) or more (e.g., 0.22 B irr or more, 0.24 B irr or more, 0.26 B irr or more, 0.28 B irr or more, 0.3 B irr or more, 0.32 B irr or more, 0.34 B irr or more, 0.36 B irr or more, 0.38 B irr or more, 0,4 B irr or more, 0.42 B irr or more, 0.44 B irr or more, 0.46 B irr or more, or 0.48 B irr or more).
  • B irr irreversibility field
  • the flux pinning force vs. field ( F p -B ) curve of the superconducting layer can peak at 0.5 times the irreversibility field ( B irr ) or less (e.g., 0.48 B irr or less, 0.46 B irr or less, 0.44 B irr or less, 0.42 B irr or less, 0.4 B irr or less, 0.38 B irr or less, 0.36 B irr or less, 0.34 B irr or less, 4.32 B irr or less, 0.3 B irr or less, 0.28 B irr or less, 0.26 B irr or less, 0.24 B irr or less, or 0.22 B irr or less).
  • B irr irreversibility field
  • the peak of the flux pinning force vs. field ( F p -B ) curve of the superconducting layer can range from any of the minimum values described above to any of the maximum values described above.
  • the flux pinning force vs. field ( F p -B ) curve of the superconducting layer can peak at from 0.2 B irr to 0.5 B irr (e.g., from 0.2 B irr to 0.36 B irr , from 0.36 B irr to 0.5 B irr , from 0.2 B irr to 0.3 B irr , from 0.3 B irr to 0.4 B irr , from 0.4 B irr to 0.5 B irr , or from 0.3 B irr to 0.5 B irr ).
  • the diameter of each subelement in the superconducting wire can be, for example, from 5 ⁇ m to 150 ⁇ m. In some examples, the diameter of each subelement in the superconducting wire can be 5 ⁇ m or more (e.g., 10 ⁇ m or more, 20 ⁇ m or more, 30 ⁇ m or more, 40 ⁇ m or more, 50 ⁇ m or more, 60 ⁇ m or more, 70 ⁇ m or more, 80 ⁇ m or more, 90 ⁇ m or more, 100 ⁇ m or more, 110 ⁇ m or more, 120 ⁇ m or more, 130 ⁇ m or more, or 140 ⁇ m or more).
  • 5 ⁇ m or more e.g., 10 ⁇ m or more, 20 ⁇ m or more, 30 ⁇ m or more, 40 ⁇ m or more, 50 ⁇ m or more, 60 ⁇ m or more, 70 ⁇ m or more, 80 ⁇ m or more, 90 ⁇ m or more, 100 ⁇ m or more, 110 ⁇ m or more, 120
  • the diameter of each subelement in the superconducting wire can be 150 ⁇ m or less (e.g., 140 ⁇ m or less, 130 ⁇ m or less, 120 ⁇ m or less, 110 ⁇ m or less, 100 ⁇ m or less, 90 ⁇ m or less, 80 ⁇ m or less, 70 ⁇ m or less, 60 ⁇ m or less, 50 ⁇ m or less, 40 ⁇ m or less, 30 ⁇ m or less, 20 ⁇ m or less, 10 ⁇ m or less).
  • 150 ⁇ m or less e.g., 140 ⁇ m or less, 130 ⁇ m or less, 120 ⁇ m or less, 110 ⁇ m or less, 100 ⁇ m or less, 90 ⁇ m or less, 80 ⁇ m or less, 70 ⁇ m or less, 60 ⁇ m or less, 50 ⁇ m or less, 40 ⁇ m or less, 30 ⁇ m or less, 20 ⁇ m or less, 10 ⁇ m or less).
  • the diameter of each subelement in the superconducting wire can range from any of the minimum values described above to any of the maximum values described above, for example from 5 ⁇ m to 150 ⁇ m (e.g., from 5 ⁇ m to 80 ⁇ m, from 80 ⁇ m to 150 ⁇ m, from 5 ⁇ m to 30 ⁇ m, from 30 ⁇ m to 60 ⁇ m, from 60 ⁇ m to 90 ⁇ m, from 90 ⁇ m to 120 ⁇ m, from 120 ⁇ m to 150 ⁇ m, or from 10 ⁇ m to 100 ⁇ m).
  • the diameter of each subelement in the superconducting wire can be, for example, from 150 ⁇ m to 500 ⁇ m.
  • superconducting wire precursors can be heat treated to prepare superconducting wires, such as those described herein.
  • tube-type superconducting wire precursors (10) can comprise a metallic matrix (for example, a Cu-based metal) (11); and at least one continuous subelement precursor (12) embedded in the matrix.
  • a metallic matrix for example, a Cu-based metal
  • the metallic matrix can comprise any suitable metal or combination of metals.
  • the metallic matrix can be formed from a metal or combination of metals that is electrically conductive at temperatures below 77 K.
  • the metal or combination of metals forming the metallic matrix can exhibit a coefficient of thermal expansion that is substantially the same or greater than the coefficient of thermal expansion of Nb 3 Sn.
  • the metallic matrix can comprise a Cu-based metal (e.g., copper or an alloy thereof).
  • each subelement precursor (12) can comprise a Sn-based metal core (25) (e.g., a Sn metal rod), a Cu-based Layer (24) coaxially disposed around the Sn-based metal core; a metal oxide layer (23) coaxially disposed around the Cu-based layer; and a Nb alloy layer (22) coaxially disposed around the metal oxide layer.
  • Sn-based metal core e.g., a Sn metal rod
  • Cu-based Layer coaxially disposed around the Sn-based metal core
  • metal oxide layer coaxially disposed around the Cu-based layer
  • Nb alloy layer coaxially disposed around the metal oxide layer.
  • Each subelement precursor (12) can further include a metallic matrix (21) disposed about the Nb alloy layer.
  • the composition of the metal oxide and the Nb alloy can be selected in combination so as to facilitate internal oxidation of the Nb alloy upon heat treatment of the superconducting wire precursor.
  • Sn from the core can diffuse to the Nb alloy layer, forming a superconducting Nb 3 Sn layer.
  • the composition of the metal oxide layer and the Nb alloy layer can be selected to provide for the formation of metal oxide particulates disposed within superconducting Nb 3 Sn layer upon heat treatment of the superconducting wire precursor.
  • the metal oxide particulates can serve to control the grain size of the Nb 3 Sn formed during heat treatment, thereby forming a niobium-tin superconducting phase comprising Nb 3 Sn grains having a refined average grain size (e.g., from 5 nm to 30 nm).
  • the Nb alloy layer can comprise an alloy of Nb and a metal that has an oxidation potential greater than the oxidation potential of Nb (e.g., Zr, Al, Ti, Be, etc.).
  • the Nb alloy layer can comprise an alloy of Nb and a metal that has a higher affinity for oxygen than Nb.
  • the Nb alloy layer can comprise a Nb alloy selected from the group consisting of a Nb-Zr alloy, a Nb-Al alloy, a Nb-Ti alloy, and combinations thereof.
  • the Nb alloy can further comprise a dopant to be incorporated into the resulting superconducting layer formed from the Nb alloy. Suitable dopants are known in the art, and include, for example, Ti, Ta, and combinations thereof.
  • the metal oxide layer can, for example, comprise a metal oxide that has a lower oxidation potential than NbO 2 .
  • the metal oxide layer can comprise a metal oxide that can supply oxygen to Nb.
  • the metal oxide layer comprises a metal oxide comprising a metal selected from the group consisting of Sn, Cu, Zn, Nb, Fe, Ni, Cr, Co, W, and combinations thereof.
  • the metal oxide layer comprises a metal oxide selected from the group consisting of SnO 2 , CuO, ZnO, Nb 2 O 5 , and combinations thereof.
  • the tube-type subelement precursor (12) can comprise a Sn-based metal core (25) (e.g., a Sn metal rod), a Cu-based layer (24) coaxially disposed around the Sn-based metal core, a first Nb alloy layer (26) coaxially disposed around the Cu-based layer, a metal oxide layer (23) coaxially disposed around the first Nb alloy layer, and a second Nb alloy layer (22) coaxially disposed around the metal oxide layer.
  • Each subelement precursor (12) can further include a metallic matrix (21) disposed about the second Nb alloy layer.
  • the first Nb alloy and the second Nb alloy can each comprise an alloy of Nb and a metal that has an oxidation potential greater than the oxidation potential of Nb (e.g., Zr, Al, Ti, Be, etc.).
  • the first Nb alloy layer and the second Nb alloy can each comprise an alloy of Nb and a metal that has a higher affinity for oxygen than Nb.
  • the first Nb alloy and the second Nb alloy can each comprise a Nb alloy selected from the group consisting of a Nb-Zr alloy, a Nb-Al alloy, a Nb-Ti alloy, and combinations thereof.
  • the first Nb alloy and/or the second Nb alloy can each optionally comprise a dopant to be incorporated into the resulting superconducting layer formed from the first Nb alloy and/or the second Nb alloy.
  • Suitable dopants are known in the art, and include, for example, Ti, Ta, and combinations thereof.
  • the metal oxide layer can, for example, comprise a metal oxide that has a lower oxidation potential than NbO 2 .
  • the metal oxide layer can comprise a metal oxide that can supply oxygen to Nb.
  • the metal oxide layer comprises a metal oxide comprising a metal selected from the group consisting of Sn, Cu, Zn, Nb, Fe, Ni, Cr, Co, W, and combinations thereof.
  • the metal oxide layer comprises a metal oxide selected from the group consisting of SnO 2 , CuO, ZnO, Nb 2 O 5 , and combinations thereof.
  • the tube-type subelement precursor (12) can comprise a Sn-based metal core (25) (e.g., a Sn metal rod), a Cu-based layer (24) coaxially disposed around the Sn-based metal core, a Nb alloy layer (22) coaxially disposed around the Cu-based layer, a metal oxide layer (23) coaxially disposed around the Cu-based layer, and a barrier layer (27) coaxially disposed around the metal oxide layer.
  • Each subelement precursor (12) can further include a metallic matrix (21) disposed about the barrier layer.
  • the Nb alloy can comprise an alloy of Nb and a metal that has an oxidation potential greater than the oxidation potential of Nb (e.g., Zr, Al, Ti, Be, etc.).
  • the Nb alloy layer can comprise an alloy of Nb and a metal that has a higher affinity for oxygen than Nb.
  • the Nb alloy layer can comprise a Nb alloy selected from the group consisting of a Nb-Zr alloy, a Nb-Al alloy, a Nb-Ti alloy, and combinations thereof.
  • the Nb alloy can further comprise a dopant to be incorporated into a resulting superconducting layer formed from the Nb alloy. Suitable dopants are known in the art, and include, for example, Ti, Ta, and combinations thereof.
  • the metal oxide layer can, for example, comprise a metal oxide that has a lower oxidation potential than NbO 2 .
  • the metal oxide layer can comprise a metal oxide that can supply oxygen to Nb.
  • the metal oxide layer comprises a metal oxide comprising a metal selected from the group consisting of Sn, Cu, Zn, Nb, Fe, Ni, Cr, Co, W, and combinations thereof.
  • the metal oxide layer comprises a metal oxide selected from the group consisting of SnO 2 , CuO, ZnO, Nb 2 O 5 , and combinations thereof.
  • the barrier layer can comprise any suitable material that can inhibit diffusion of the superconducting layer into the metallic matrix.
  • the barrier layer can comprise Nb metal or an alloy thereof, Ta metal or an alloy thereof, Ti metal or an alloy thereof, Mo metal or an alloy thereof, or a combination thereof.
  • the barrier layer can comprise Nb metal or an alloy thereof.
  • the barrier layer can comprise a Nb alloy.
  • the Nb alloy can comprise an alloy formed from Nb and a metal that has an oxidation potential greater than the oxidation potential of Nb.
  • the Nb alloy can comprise an alloy formed from Nb and a metal that is less noble than Nb (e.g., a metal that appears lower than Nb in a galvanic series).
  • suitable Nb alloys include, but are not limited to, Nb-Zr alloys, Nb-Al alloys, Nb-Ti alloys, Nb-Ta alloys, Nb-Be alloys, Nb-Ni alloys, Nb-Fe alloys, Nb-Sn alloys, and combinations thereof.
  • the Nb alloy can be selected from the group consisting of a Nb-Zr alloy, a Nb-Al alloy, a Nb-Ti alloy, and combinations thereof.
  • Precursors of this type can be fabricated using standard methods known in the art for fabricating tube-type superconducting strands.
  • the metal oxide layers in the precursors above can be introduced into the tube-type superconducting wire precursor preforms by positioning a metal oxide powder at an appropriate position between two layers of the tube-type superconducting wire precursor preform.
  • the metal oxide layer can be introduced into the tube-type superconducting wire precursor preforms by positioning a metal oxide powder between the outer surface of the Cu-based tube forming the Cu-based layer and the inner surface of the Nb alloy tube forming the Nb alloy layer.
  • the metal oxide layers in the precursors above can also be introduced into the tube-type superconducting wire precursor preforms by applying a metal oxide coating to an appropriate surface of the tube-type superconducting wire precursor preform.
  • the metal oxide layer can be introduced into the tube-type superconducting wire precursor preforms by applying a metal oxide coating to the outer surface of the Cu-based tube forming the Cu-based layer, the inner surface of the Nb alloy tube forming the Nb alloy layer, or a combination thereof.
  • the metal oxide coating can be applied using any suitable method, such as spraying, dip coating, vapor coating, or electrolytic coating.
  • the preforms can be formed into a wire by first extruding the preform, followed by either wire-drawing or swaging the extruded preform. Once drawn or swaged, the preform can be re-stacked by repeating the extrusion step, followed by the drawing or swaging steps, to achieve the desired wire diameter. The re-stacking step can be repeated as many times as necessary until the desired wire diameter is obtained.
  • powder-in-tube type superconducting wire precursors can comprise a metallic matrix (for example, a Cu-based metal), and at least one continuous subelement precursor (40) embedded in the matrix.
  • Each subelement precursor can, for example, comprise a core (43) comprising a blend of a Sn-containing powder and a metal oxide powder, and a Nb alloy layer (42) coaxially disposed around the core.
  • Each subelement precursor (40) can further include a metallic matrix (41) disposed about the Nb alloy layer.
  • the composition of the metal oxide powder and the Nb alloy can be selected in combination so as to facilitate internal oxidation of the Nb alloy upon heat treatment of the superconducting wire precursor.
  • Sn from the Sn-containing powder present in the core can diffuse to the Nb alloy layer, forming the superconducting Nb 3 Sn layer.
  • the composition of the metal oxide powder and the Nb alloy layer can be selected to provide for the formation of metal oxide particulates disposed within superconducting Nb 3 Sn layer upon heat treatment of the superconducting wire precursor.
  • the metal oxide particulates can serve to control the grain size of the Nb 3 Sn formed during heat treatment, thereby forming a niobium-tin superconducting phase comprising Nb 3 Sn grains having a refined average grain size (e.g., from 5 nm to 30 nm).
  • the Nb alloy layer can comprise an alloy of Nb and a metal that has an oxidation potential greater than the oxidation potential of Nb (e.g., Zr, Al, Ti, Be, etc.).
  • the Nb alloy can comprise an alloy of Nb and a metal that is less noble than Nb (e.g., a metal that appears lower than Nb in a galvanic series).
  • the Nb alloy layer can comprise a Nb alloy selected from the group consisting of a Nb-Zr alloy, a Nb-Al alloy, a Nb-Ti alloy, and combinations thereof.
  • the Nb alloy can further comprise a dopant to be incorporated into the resulting superconducting layer formed from the Nb alloy. Suitable dopants are known in the art, and include, for example, Ti, Ta, and combinations thereof.
  • the core can comprise a homogeneous blend of a Sn-containing powder and a metal oxide powder.
  • the metal oxide powder can, for example, comprise a metal oxide that has a lower oxidation potential than NbO 2 .
  • the metal oxide powder can comprise a metal oxide that can supply oxygen to Nb.
  • the metal oxide powder comprises a metal oxide comprising a metal selected from the group consisting of Sn, Cu, Zn, Nb, Fe, Ni, Cr, Co, W, and combinations thereof.
  • the metal oxide powder comprises a metal oxide selected from the group consisting of SnO 2 , CuO, ZnO, Nb 2 O 5 , and combinations thereof.
  • the Sn-containing powder can, for example, comprise Sn powder, NbSn 2 powder, Nb 6 Sn 5 powder, or a combination thereof.
  • the Sn-containing powder can further comprise Cu powder.
  • the addition of Cu to the powder core can have a catalytic effect for the formation of Nb 3 Sn, and can reduce the reaction temperature necessary to form the superconducting phase upon heat treatment.
  • the Sn powder can comprise from greater than 0 wt. % to 10 wt. % Cu powder, based on the total weight of all of the components in the powder core.
  • Precursors of this type can be fabricated using standard methods known in the art for fabricating powder-in-tube type superconducting strands. Once formed, the preforms can be formed into a wire by first extruding the preform, followed by either wire-drawing or swaging the extruded preform. Once drawn or swaged, the preform can be re-stacked by repeating the extrusion step, followed by the drawing or swaging steps, to achieve the desired wire diameter. The re-stacking step can be repeated as many times as necessary until the desired wire diameter is obtained.
  • the precursors can comprise a metallic matrix (for example, a Cu-based metal), and at least one continuous subelement precursor embedded in the matrix.
  • Each subelement precursor can, for example, comprise a Sn-based metal core; a Cu-based layer coaxially disposed around the Sn-based metal core; a Nb alloy layer coaxially disposed around the Cu-based layer, the Nb alloy layer further comprising a plurality of metal oxide regions disposed within the Nb alloy layer; and a barrier layer coaxially disposed around the Nb alloy layer.
  • Each subelement precursor can further include a metallic matrix disposed about the barrier layer.
  • the Nb alloy layer can comprise a plurality of discrete Nb alloy rods which in combination make up the Nb alloy layer.
  • Each Nb alloy rod can comprise a Nb alloy core ensheathed in copper or a copper alloy.
  • the Nb alloy rods can be formed into hexed cross sectioned rods to facilitate hexagonal packing of the Nb alloy rods.
  • the plurality of metal oxide regions can comprise a plurality of metal oxide rods.
  • Each metal oxide rod can comprise a metal oxide core (e.g., a metal oxide powder) ensheathed in copper or a copper alloy.
  • the metal oxide rods can also be formed into hexed cross sectioned rods to enable their packing among the hexagonally packed Nb alloy rods.
  • the superconducting wire precursors can comprise a metallic matrix (for example, a Cu-based metal), and at least one continuous subelement precursor (50) embedded in the matrix.
  • Each subelement can comprise a Sn-based metal core (51) (e.g., a Sn metal rod), a Cu-based layer (56) coaxially disposed around the Sn-based metal core, a plurality of stacked Cu (55) -encased Nb alloy rods (54) disposed around the Cu-based layer, and a barrier layer (53) coaxially disposed around the stacked Nb alloy rods.
  • a plurality of metal oxide regions (57) can be disposed within the stacked Cu (55) -encased Nb alloy rods.
  • the metal oxide regions (57) can each comprise a metal oxide powder.
  • Each subelement precursor (50) can further include a metallic matrix (52) disposed about the barrier layer.
  • the composition of the metal oxide and the Nb alloy can be selected in combination so as to facilitate internal oxidation of the Nb alloy upon heat treatment of the superconducting wire precursor.
  • Sn from the core can diffuse to the Nb alloy layer (e.g., to the stacked Cu-encased Nb alloy rods), forming a superconducting Nb 3 Sn layer (e.g., a plurality of stacked Cu-encased Nb 3 Sn rods).
  • the composition of the metal oxide layer and the Nb alloy layer can be selected to provide for the formation of metal oxide particulates disposed within superconducting Nb 3 Sn upon heat treatment of the superconducting wire precursor.
  • the metal oxide particulates can serve to control the grain size of the Nb 3 Sn formed during heat treatment, thereby forming a niobium-tin superconducting phase comprising Nb 3 Sn grains having a refined average grain size (e.g., from 5 nm to 30 nm).
  • the Nb alloy layer (e.g., the Nb alloy forming the Nb alloy rods) can comprise an alloy of Nb and a metal that has an oxidation potential greater than the oxidation potential of Nb (e.g., Zr, Al, Ti, Be, etc.).
  • the Nb alloy layer can comprise an alloy of Nb and a metal that is less noble than Nb (e.g., a metal that appears lower than Nb in a galvanic series).
  • the Nb alloy layer (e.g., the Nb alloy forming the Nb alloy rods) can comprise a Nb alloy selected from the group consisting of a Nb-Zr alloy, a Nb-Al alloy, a Nb-Ti alloy, and combinations thereof.
  • the Nb alloy (e.g., the Nb alloy forming the Nb alloy rods) can further comprise a dopant to be incorporated into a resulting superconducting phase formed from the Nb alloy. Suitable dopants are known in the art, and include, for example, Ti, Ta, and combinations thereof.
  • the plurality of metal oxide regions can, in some examples, each comprise a metal oxide that has a lower oxidation potential than NbO 2 . In some examples, the plurality of metal oxide regions can each comprise a metal oxide that can supply oxygen to Nb. In some examples, the plurality of metal oxide regions each comprise a metal oxide comprising a metal selected from the group consisting of Sn, Cu, Zn, Nb, Fe, Ni, Cr, Co, W, and combinations thereof. In some examples, the plurality of metal oxide regions each comprise a metal oxide selected from the group consisting of SnO 2 , CuO, ZnO, Nb 2 O 5 , and combinations thereof.
  • the barrier layer can comprise any suitable material that can inhibit diffusion of the superconducting layer into the metallic matrix.
  • the barrier layer can comprise Nb metal or an alloy thereof, Ta metal or an alloy thereof, Ti metal or an alloy thereof, Mo metal or an alloy thereof, or a combination thereof.
  • the barrier layer can comprise Nb metal or an alloy thereof.
  • the barrier layer can comprise a Nb alloy.
  • suitable Nb alloys include, but are not limited to, Nb-Zr alloys, Nb-Al alloys, Nb-Ti alloys, Nb-Ta alloys, Nb-Be alloys, Nb-Ni alloys, Nb-Fe alloys, Nb-Sn alloys, and combinations thereof.
  • the Nb alloy can be selected from the group consisting of a Nb-Zr alloy, a Nb-Al alloy, a Nb-Ti alloy, and combinations thereof.
  • the Nb alloy layer can comprise a plurality of discrete Nb alloy rods, each Nb alloy rod comprising a Nb alloy core ensheathed in copper or a copper alloy.
  • the Nb alloy rods are formed into hexed cross sectioned rods, and the Nb alloy layer comprises a plurality of hexagonally packed Nb alloy rods.
  • the plurality of metal oxide regions can comprise a plurality of metal oxide rods, each metal oxide rod comprising a metal oxide core ensheathed in copper or a copper alloy.
  • the metal oxide core can, for example, comprise a metal oxide powder.
  • the metal oxide rods are formed into hexed cross sectioned rods to enable their packing among the hexagonally packed Nb alloy rods.
  • Precursors of this type can be fabricated using standard rod-restack-processes known in the art. See, for example, U.S. Patent No. 6,981,309 , which is hereby incorporated by reference in its entirety.
  • the preforms can be formed into a wire by first extruding the preform, followed by either wire-drawing or swaging the extruded preform. Once drawn or swaged, the preform can be re-stacked by repeating the extrusion step, followed by the drawing or swaging steps, to achieve the desired wire diameter. The re-stacking step can be repeated as many times as necessary until the desired wire diameter is obtained.
  • Also disclosed herein are methods of making superconducting wires comprising heat treating any of the superconducting wire precursors described herein under conditions effective to form a superconducting wire comprising a superconducting phase comprising Nb 3 Sn.
  • Heat treating the superconducting wire precursor can, for example, comprise heating the superconducting wire precursor at a temperature of at least 600°C (e.g., 625°C or more, 650°C or more, 675°C or more, 700°C or more, 725°C or more, 750°C or more, 775°C or more, 800°C or more, or 825°C or more).
  • 600°C e.g., 625°C or more, 650°C or more, 675°C or more, 700°C or more, 725°C or more, 750°C or more, 775°C or more, 800°C or more, or 825°C or more.
  • heat treating the superconducting wire precursor can comprise heating the superconducting wire precursor at a temperature of 850°C or less (e.g., 825°C or less, 800°C or less, 775°C or less, 750°C or less, 725°C or less, 700°C or less, 675°C or less, 650°C or less, or 625°C or less).
  • 850°C or less e.g. 825°C or less, 800°C or less, 775°C or less, 750°C or less, 725°C or less, 700°C or less, 675°C or less, 650°C or less, or 625°C or less.
  • the temperature at which the superconducting wire precursor is heated during heat treatment can range from any of the minimum values described above to any of the maximum values described above, for example from 600°C to 850°C (e.g., from 600°C to 725°C, from 725°C to 850°C, from 600°C to 650°C, from 650°C to 700°C, from 700°C to 750°C, from 750°C to 800°C, from 800°C to 850°C, or from 650°C to 800°C).
  • 600°C to 850°C e.g., from 600°C to 725°C, from 725°C to 850°C, from 600°C to 650°C, from 650°C to 700°C, from 700°C to 750°C, from 750°C to 800°C, from 800°C to 850°C, or from 650°C to 800°C.
  • Heat treating the superconducting wire precursor can, for example, comprise heating the superconducting wire precursor for at least 10 minutes (e.g., 20 minutes or more, 30 minutes or more, 40 minutes or more, 50 minutes or more, 1 hour or more, 2 hours or more, 3 hours or more, 4 hours or more, 5 hours or more, 10 hours or more, 20 hours or more, 30 hours or more, 40 hours or more, 50 hours or more, 60 hours or more, 70 hours or more, 80 hours or more, 90 hours or more, 100 hours or more, 200 hours or more, 300 hours or more, 400 hours or more, 500 hours or more, 600 hours or more, or 700 hours or more).
  • 10 minutes e.g., 20 minutes or more, 30 minutes or more, 40 minutes or more, 50 minutes or more, 1 hour or more, 2 hours or more, 3 hours or more, 4 hours or more, 5 hours or more, 10 hours or more, 20 hours or more, 30 hours or more, 40 hours or more, 50 hours or more, 60 hours or more, 70 hours or more, 80 hours or more
  • heat treating the superconducting wire precursor can comprise heating the superconducting wire precursor for 800 hours or less (e.g., 700 hours or less, 600 hours or less, 500 hours or less, 400 hours or less, 300 hours or less, 200 hours or less, 100 hours or less, 90 hours or less, 80 hours or less, 70 hours or less, 60 hours or less, 50 hours or less, 40 hours or less, 30 hours or less, 20 hours or less, 10 hours or less, 5 hours or less, 4 hours or less, 3 hours or less, 2 hours or less, 1 hour or less, 50 minutes or less, 40 minutes or less, 30 minutes or less, or 20 minutes or less).
  • 800 hours or less e.g., 700 hours or less, 600 hours or less, 500 hours or less, 400 hours or less, 300 hours or less, 200 hours or less, 100 hours or less, 90 hours or less, 80 hours or less, 70 hours or less, 60 hours or less, 50 hours or less, 40 hours or less, 30 hours or less, 20 hours or less, 10 hours or less, 5 hours or less, 4
  • the time for which the superconducting wire precursor is heat treated can range from any of the minimum values described above to any of the maximum values described above, for example for from 10 minutes to 800 hours (e.g., from 10 minutes to 400 hours, from 400 hours to 800 hours, from 10 minutes to 200 hours, from 200 hours to 400 hours, from 400 hours to 600 hours, from 600 hours to 800 hours, from 10 minutes to 100 hours, or from 100 hours to 700 hours).
  • 10 minutes to 800 hours e.g., from 10 minutes to 400 hours, from 400 hours to 800 hours, from 10 minutes to 200 hours, from 200 hours to 400 hours, from 400 hours to 600 hours, from 600 hours to 800 hours, from 10 minutes to 100 hours, or from 100 hours to 700 hours).
  • the superconducting wires described herein can be formed into similar electrically conducting structures, including, but not limited to, flattened tapes, laminated wires formed from multiple wires, and wound multi-wire cables.
  • Applications for superconducting wires are known in the art, and include, for example, electromagnetic devices such as, but not limited to: superconducting magnets, such as those described in U.S. Patent No. 6,172,588 to Laskaris et al. which is incorporated herein by reference in its entirety; motors; transformers; and generators.
  • Such electromagnetic devices may in turn be incorporated into larger systems, such as, for example, magnetic resonance imaging systems, particle accelerators, and fusion reactors.
  • the Nb alloy can be any Nb alloy where the additional element or elements can be oxidized internally, for example Nb-Zr or Nb-Al.
  • the Nb alloy can also include other components that are not oxidized and that can increase the superconductivity potential, such as Nb doped with Ti, or Nb doped with Ta.
  • An oxide powder can be positioned in the subelements so that during heat treatment the Nb alloy can reduce the oxide powder and take up the oxygen.
  • Nb-Zr or Nb-Al alloys can form fine intra-granular and inter-granular ZrO 2 or Al 2 O 3 precipitates in the Nb 3 Sn matrix.
  • the ZrO 2 or Al 2 O 3 precipitates can refine the Nb 3 Sn grain size (e.g., by a factor of three for a heat treatment temperature of 625°C).
  • the refined grain size of the Nb 3 Sn ( ⁇ 30 nm) can shift the peak of the flux pinning force vs. field ( F p -B ) curve towards half of the irreversibility field ( Birr ), and can improve the high-field J c (e.g., by a factor of two for a heat treatment temperature of 625°C).
  • Nb 3 Sn superconductors can be used in applications such as nuclear magnetic resonance (NMR), fusion reactors, and particle accelerator magnets. Such applications can require high critical current density ( J c ) at magnetic fields from 12 T to 20 T or more.
  • Nb 3 Sn strands At present there are three types of Nb 3 Sn strands that have been reported to have a J c of ⁇ 5000 A/mm 2 at 4.2 K and 12 T, namely "rod-restack-process" ( See, for example, U.S. Patent Application Publication No. 2006/0081307 ), "powder-in-tube", and "tube type".
  • Each of the Nb 3 Sn strands is composed of a plurality of superconductor units (named "subelements") embedded in a Cu matrix.
  • a subelement of a rod-restack-process strand can contain a Cu-encased Sn core, which can be surrounded by a plurality of Cu-encased Nb alloy rods, a Nb barrier, and another Cu layer.
  • a subelement of a powder-in-tube strand can be a Cu-jacketed Nb alloy tube filled by Sn-source powders (such as Cu 5 Sn 4 or a mixture of NbSn 2 and Cu powders).
  • Sn-source powders such as Cu 5 Sn 4 or a mixture of NbSn 2 and Cu powders.
  • a tube type strand is similar to a powder-in-tube strand, but uses a Cu-encased Sn rod as the Sn source instead of Sn-containing powders.
  • Nb 3 Sn grain size can improve the high-field J c of the Nb 3 Sn superconductors.
  • Nb 3 Sn conductors with grain sizes of typically 100-200 nm, have bulk pinning force vs. field curves ( F p -B ) that peak at 0.2 of the irreversibility field ( B irr ).
  • F p -B bulk pinning force vs. field curves
  • B irr the irreversibility field
  • the shift of the F p -B curve peak to 0.5 B irr can improve the high-field (> 10 T) J c , which can push the application range of Nb 3 Sn conductors to higher fields (> 20 T).
  • One report showed that a reduction of the Nb 3 Sn grain size improved the 12 T J c value by a factor of three.
  • the shift of the F p -B curve peak to 0.5 B irr can also reduce the value of J c below 2 T, which can reduce low-field magnetization and improve the stability of the Nb 3 Sn conductors.
  • a heat treatment at 600-800°C can transform precursors, including Sn, Cu, and Nb metals or alloys thereof in a green-state wire to the Nb 3 Sn phase through a diffusion reaction process.
  • 615°C can only refine the grain size to about 90 nm.
  • Nb 3 Sn films An internal oxidation method that was successfully used in Nb 3 Sn films offers an alternative.
  • the film approach used a Nb-Zr foil which was first anodized to form a Nb 2 O 5 layer on the surface and then annealed to decompose the Nb 2 O 5 and dissolve oxygen in the Nb-Zr alloy; after being coated with Cu-Sn, the foil was reacted at 1050°C to form Nb 3 Sn with ZrO 2 precipitates. It was reported that with sufficient oxygen supply, the Nb 3 Sn grain size could be refined by an order of magnitude.
  • Nb 3 Sn wire is different from a film.
  • a Nb 3 Sn wire has a cross section which can facilitate cabling.
  • the Nb 3 Sn wire has a peripheral Cu matrix in which all subelements are embedded.
  • several deformations are usually performed on a green-state Nb 3 Sn wire to obtain a small subelement diameter (typically ⁇ 60 ⁇ m), while such deformations are not needed for the fabrication of a film. Due to these deformations, the precursors to compose a Nb 3 Sn wire must be sufficiently ductile: it is this point that hinders the transfer of the technique developed for films to the processes for forming wires.
  • Nb 3 Sn strands e.g., tube type, powder-in-tube, and rod-restack-process
  • All of these strands used a metal oxide powder as the oxygen source, and the oxide powder was located in a position inside each subelement so that it can release sufficient oxygen to oxidize the Zr or Al atoms in the Nb-Zr or Nb-Al alloy during the heat treatment.
  • the fine ZrO 2 or Al 2 O 3 particles precipitated in the Nb 3 Sn matrix refined the Nb 3 Sn grain size and boosted the high-field J c of these strands.
  • each subelement was fabricated with a Nb alloy (herein denoted as Nb-M) that can be internally oxidized.
  • the Nb alloy can have additional elements that are not oxidized, such as Ti or Ta, and that can increase the superconductor potential.
  • each subelement contained an oxygen source that can supply oxygen to the Nb-M alloy during heat treatment.
  • Metal M in the Nb-M alloy can have sufficient solubility in Nb so that it can form a Nb-M solid solution with a sufficient amount of M.
  • Metal M can be less noble than Nb so that during heat treatment the metal M is oxidized while Nb itself is left behind for the formation of NbsSn. Furthermore, the less noble a metal is, the finer its oxide precipitates (e.g., the internal oxidation products) are.
  • Ti, Zr and Al can all be used as the metal M, meaning the Nb-M alloy can be Nb-Ti, Nb-Zr, or Nb-Al, which would result in TiO 2 , ZrO 2 , and Al 2 O 3 precipitates, respectively.
  • the oxygen source was introduced into the strands discussed herein by adding a metal oxide powder into the subelements, taking advantage of the good flowability of powders during the drawing process.
  • a metal oxide powder For Nb 3 Sn strands, Cu was used as a matrix, but also inside the subelements, because Cu destabilizes high-Sn Nb-Sn compounds and promotes Nb 3 Sn formation.
  • calculations show that the diffusion rate of oxygen in Cu can be very slow because of the low oxygen solubility in Cu. Thus, for the design of the subelement structure for internal oxidation, having oxygen diffuse through a thick Cu layer was avoided.
  • the subelement (12) is comprised of five concentric layers, namely, the Cu matrix (21), the Nb-Zr or Nb-Al alloy tube (22), the oxide layer (23), the Cu layer (24), and the central Sn rod (25).
  • the oxide layer (23) is located between the Cu layer (24) and the Nb alloy tube (22) so that the Nb alloy can reduce the oxide powder and take up the oxygen during heat treatment. If the oxide powder was located between the Cu layer (24) and the central Sn rod (25), excess heat treatment time can be needed to supply sufficient amount of oxygen to Nb-Zr alloy through the Cu layer (24).
  • the wire (10) comprises a plurality of subelements (12), as well as Cu matrix (11), and can further comprise a certain number of Cu hexagons (13), which can be located in the center of the wire (10) to ease wire drawing.
  • Figure 1 shows a schematic view of an exemplary configuration, and is not meant to be limiting.
  • the wire can include any number of subelements (e.g., over a hundred).
  • Heat treatment of the tube type subelement (12) in Figure 2 can convert the subelements to those as shown in Figure 3 .
  • the heat treatment can transform the oxide layer (23), the Cu layer (24), and the central Sn rod (25) in Figure 2 to the non-superconducting core (34) in Figure 3 .
  • the subelement (30) of Figure 3 further comprises a superconducting Nb 3 Sn layer (33) with ZrO 2 or Al 2 O 3 particles formed therein, and a layer of Nb-Zr or Nb-Al alloy (32) is left unreacted to protect the Cu matrix (31).
  • the metal oxide In order for the metal oxide powder to be reduced by the Nb alloy, the metal oxide should be less stable than Nb oxide.
  • metal oxides that can supply oxygen to the Nb alloy include, but are not limited to, SnO 2 , ZnO, Nb 2 O 5 , and CuO.
  • SnO 2 powder can, for example, supply its oxygen to the Nb alloy until the SnO 2 completely exhausts its oxygen content and turns into liquid Sn.
  • Nb 2 O 5 can only supply a portion of its oxygen to the Nb alloy while the Nb 2 O 5 powder transforms to NbO 2 , which cannot supply oxygen to the Nb alloy.
  • the oxide is too unstable (e.g., CuO)
  • the rate at which the oxygen is supplied by this oxide can be faster than the rate at which the oxygen diffuses deeper into the Nb alloy, making the oxygen content at the Nb alloy surface rise with time.
  • a sufficient oxygen content at the Nb alloy surface can oxidize both Nb and Zr non-selectively, which is adverse to the formation of Nb 3 Sn.
  • Such issues are more frequently observed at higher heat treatment temperatures.
  • a pre-heat treatment stage at a lower temperature e.g., 500°C
  • a more stable oxide e.g., Nb 2 O 5
  • Figure 4 displays an example powder-in-tube subelement for the realization of internal oxidation.
  • the subelement (40) is comprised of a Cu (41) -jacketed Nb-Zr or Nb-Al alloy tube (42), which is filled with a mixture (43) of a metal oxide powder and a Cu-Sn or Nb-Sn intermetallic powder, which can serve as the Sn source.
  • the metal oxide powder in the core can release oxygen for the Nb alloy (42) to be internally oxidized.
  • experiments demonstrated that the oxide powder does not need to contact the Nb alloy to supply oxygen.
  • a metal oxide powder like SnO 2 or Nb 2 O 5 can supply oxygen to Nb alloy through the atmosphere.
  • the metal oxide powder in the core can be blended with the Sn-source powder and thus does not contact the Nb alloy tube, but it can still supply oxygen to Nb alloy.
  • a Nb 6 Sn 5 or Nb 3 Sn phase begins to form at the inner surface of the Nb alloy tube (42)
  • the newly formed Nb 6 Sn 5 or Nb 3 Sn layer can cut off the connection between the oxide powder and the unreacted Nb alloy, and thus terminate the oxygen transfer process. This can be avoided by adding a pre-heat treatment stage at a lower temperature (e.g., 500°C), which can allow oxygen transfer but postpones the formation of the Nb 6 Sn 5 or Nb 3 Sn phase.
  • a pre-heat treatment stage at a lower temperature (e.g., 500°C), which can allow oxygen transfer but postpones the formation of the Nb 6 Sn 5 or Nb 3 Sn phase
  • Figure 5 displays a schematic representation of a modified rod-restack-process subelement (50) that enables internal oxidation.
  • the subelement (50) comprises a Sn core (51), a Cu can (56), a Nb alloy barrier (53), a Cu matrix (52), and a stacking of Cu (55) -encased Nb-Zr or Nb-Al alloy rods (54), a certain number of which are replaced by a metal oxide powder (57).
  • the diffusion rate of oxygen through the Cu layer is slow, so supplying oxygen through a thick Cu layer tends to cause an insufficient amount of oxygen for oxidizing the Zr or Al atoms in the Nb-Zr or Nb-Al alloy.
  • the thickness of the Cu layer among the Nb alloy rods (54) is small (e.g., less than 1 ⁇ m), which can allow rapid transfer of oxygen from the oxide powder to the surrounding Nb alloy rods.
  • CuO powder can be used as the metal oxide powder.
  • the Nb alloy used for the tube (22) was commercial Nb-1Zr, and the oxide powder used was SnO 2 .
  • the outer diameter of the Nb-1Zr tube in the final-size subelement was 0.22 mm.
  • the wire was heat treated at 625°C for 800 hours. It was found that over 3 atomic percent (at. %) oxygen was taken up by the Nb-Zr alloy after the heat treatment.
  • An SEM image displaying the Nb 3 Sn grains of this wire is shown in Figure 6 .
  • Nb 3 Sn grain size was about 36 nm, which is about a third of the present Nb 3 Sn strands reacted at 625°C (100-110 nm).
  • the 4.2 K, 12 T Nb 3 Sn-layer J c of this wire was 9600 A/mm 2 , which is almost double the value of the present state-of-the-art Nb 3 Sn strands ( ⁇ 5000 A/mm 2 ).
  • the peak of the F p -B curve of this wire shifted to 0.34 B irr .
  • the grain size can be further reduced with the use of even lower reaction temperatures (e.g., 605°C), or higher Zr content (e.g., 1.5%) to produce a greater density of ZrO 2 particles.
  • a Nb-Al solid solution which is a ductile alloy, can give a different distribution of oxide particles and can affect the grain size refinement differently.
  • compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of a few aspects of the claims. Any compositions and methods that are functionally equivalent are intended to be included insofar as they fall within the scope of the claims. Various modifications of the compositions and methods in addition to those shown and described herein are intended to be included insofar as they fall within the scope of the appended claims. Further, while only certain representative compositions and methods disclosed herein are specifically described, other compositions and methods also are intended to be included insofar as they fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein or less, however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated.

Claims (15)

  1. Fil supraconducteur comprenant :
    une matrice comprenant un métal à base de Cu ; et
    au moins un sous-élément continu incrusté dans la matrice ;
    dans lequel chaque sous-élément comprend :
    un noyau non supraconducteur ;
    une couche supraconductrice disposée de manière coaxiale autour du noyau non supraconducteur ; et
    une couche barrière disposée de manière coaxiale autour de la couche supraconductrice ;
    caractérisé en ce que
    la couche supraconductrice comprend une pluralité de grains de Nb3Sn stabilisés par des particules d'oxyde métallique disposées à l'intérieur, et
    dans lequel les grains de Nb3Sn ont une taille moyenne de grain de 5 nm à 90 nm.
  2. Fil supraconducteur selon la revendication 1, dans lequel les grains de Nb3Sn ont une taille moyenne de grain de 15 nm à 50 nm.
  3. Fil supraconducteur selon l'une quelconque des revendications 1 et 2, dans lequel la couche supraconductrice comprend en outre un dopant.
  4. Fil supraconducteur selon la revendication 3, dans lequel le dopant comprend du Ti, du Ta, ou une combinaison de ceux-ci.
  5. Fil supraconducteur selon l'une quelconque des revendications 1 à 4, dans lequel la couche supraconductrice présente une densité de courant critique (Jc ) à champ élevé de 5000 à 21 000 A/mm2 à une température de 4,2 K dans un champ magnétique de 12 T.
  6. Fil supraconducteur selon l'une quelconque des revendications 1 à 5, dans lequel la couche supraconductrice présente une courbe de force d'épinglage de flux en fonction du champ (Fp-B) qui culmine à 0,2 à 0,5 fois le champ d'irréversibilité (Birr ).
  7. Fil supraconducteur selon l'une quelconque des revendications 1 à 6, dans lequel la couche barrière comprend un alliage de Nb, un alliage de Ta, un alliage de Ti, ou une combinaison de ceux-ci.
  8. Fil supraconducteur selon la revendication 7, dans lequel la couche barrière comprend un alliage de Nb, et l'alliage de Nb comprend un alliage de Nb et un métal qui présente un potentiel d'oxydation supérieur au potentiel d'oxydation de Nb.
  9. Fil supraconducteur selon la revendication 7 ou 8, dans lequel la couche barrière comprend un alliage de Nb, et l'alliage de Nb est sélectionné dans le groupe consistant en un alliage de Nb-Zr, un alliage de Nb-AI, un alliage de Nb-Ti, et les combinaisons de ceux-ci.
  10. Fil supraconducteur selon l'une quelconque des revendications 1 à 9, dans lequel les particules d'oxyde métallique comprennent un métal qui présente un potentiel d'oxydation supérieur au potentiel d'oxydation de Nb.
  11. Fil supraconducteur selon l'une quelconque des revendications 1 à 10, dans lequel les particules d'oxyde métallique comprennent un oxyde métallique sélectionné dans le groupe consistant en ZrO2, Al2O3, TiO2, et les combinaisons de ceux-ci.
  12. Fil supraconducteur selon l'une quelconque des revendications 1 à 11, dans lequel le diamètre de chaque sous-élément est de 5 µm à 150 µm.
  13. Précurseur de fil supraconducteur comprenant :
    une matrice comprenant un métal à base de Cu ; et
    au moins un précurseur de sous-élément continu incrusté dans la matrice ;
    dans lequel chaque précurseur de sous-élément comprend un précurseur de sous-élément comprenant l'un quelconque parmi :
    (1) un noyau métallique à base de Sn ; une couche à base de Cu disposée de manière coaxiale autour du noyau métallique à base de Sn ; une couche d'oxyde métallique disposée de manière coaxiale autour de la couche à base de Cu ; et une couche d'alliage de Nb disposée de manière coaxiale autour de la couche d'oxyde métallique ;
    (2) un noyau métallique à base de Sn ; une couche à base de Cu disposée de manière coaxiale autour du noyau métallique à base de Sn ; une première couche d'alliage de Nb disposée de manière coaxiale autour de la couche à base de Cu ; une couche d'oxyde métallique disposée de manière coaxiale autour de la première couche d'alliage de Nb ; et une seconde couche d'alliage de Nb disposée de manière coaxiale autour de la couche d'oxyde métallique ;
    (3) un noyau métallique à base de Sn ; une couche à base de Cu disposée de manière coaxiale autour du noyau métallique à base de Sn ; une couche d'alliage de Nb disposée de manière coaxiale autour de la couche à base de Cu ; une couche d'oxyde métallique disposée de manière coaxiale autour de la couche d'alliage de Nb ; et une couche barrière disposée de manière coaxiale autour de la couche d'oxyde métallique ;
    (4) un noyau comprenant un mélange d'une poudre contenant du Sn et d'une poudre d'oxyde métallique ; et une couche d'alliage de Nb disposée de manière coaxiale autour du noyau ; ou
    (5) un noyau métallique à base de Sn ; une couche à base de Cu disposée de manière coaxiale autour du noyau métallique à base de Sn ; une couche d'alliage de Nb disposée de manière coaxiale autour de la couche à base de Cu, la couche d'alliage de Nb comprenant en outre une pluralité de régions d'oxyde métallique disposées à l'intérieur de la couche d'alliage de Nb ; et une couche barrière disposée de manière coaxiale autour de la couche d'alliage de Nb.
  14. Procédé de fabrication d'un fil supraconducteur comprenant le traitement thermique du précurseur de fil supraconducteur selon la revendication 13 pour former un fil supraconducteur comprenant une phase supraconductrice comprenant du Nb3Sn.
  15. Procédé selon la revendication 14, dans lequel le traitement thermique du précurseur de fil supraconducteur comprend le chauffage du précurseur de fil supraconducteur à une température d'au moins 600 °C, le chauffage du précurseur de fil supraconducteur pendant au moins 10 minutes, ou une combinaison de ceux-ci.
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US10317485B2 (en) * 2016-10-28 2019-06-11 General Electric Company System and method for magnetic resonance imaging one or more subjects
EP3355373B1 (fr) * 2017-01-25 2021-03-03 Bruker OST LLC Amélioration de la densité de courant critique de brins dans des brins supraconducteurs nb3sn au moyen d'un nouveau traitement thermique
WO2018198515A1 (fr) * 2017-04-27 2018-11-01 国立研究開発法人物質・材料研究機構 Procédé de production de tige d'enroulement supraconductrice au nb3sn, précurseur de tige d'enroulement supraconductrice au nb3sn, et tige d'enroulement supraconductrice au nb3sn les utilisant
CN108432735A (zh) * 2018-05-21 2018-08-24 江苏智研科技有限公司 一种颗粒状农产品表面杀虫灭菌装置及杀虫灭菌的方法
DE102018126760B4 (de) 2018-10-26 2020-08-13 Bruker Eas Gmbh Monofilament zur Herstellung eines Nb3Sn-haltigen Supraleiterdrahts, insbesondere für eine interne Oxidation
DE102019209170A1 (de) 2019-06-25 2020-12-31 Bruker Eas Gmbh Subelement auf Basis von Nb-haltigen Stabelementen mit pulvergefülltem Kernrohr für einen Nb3Sn-haltigen Supraleiterdraht und zugehörige Herstellungsverfahren
WO2021133193A1 (fr) * 2019-12-26 2021-07-01 Акционерное Общество "Твэл" Ebauche pour produire un conducteur supraconducteur de grande longueur à base de nb3sn
CN113373404B (zh) * 2021-06-10 2022-09-27 中国科学院近代物理研究所 一种铜基厚壁Nb3Sn薄膜超导腔及其制备方法
WO2023146540A1 (fr) * 2022-01-30 2023-08-03 Fermi Research Alliance, Llc Ensemble barrière bicouche pour supraconducteur à base de fer et procédés associés
CN114664495A (zh) * 2022-05-23 2022-06-24 西部超导材料科技股份有限公司 一种内稳定型青铜法Nb3Sn超导线材及其制备方法
CN115295242B (zh) * 2022-09-30 2023-01-24 西部超导材料科技股份有限公司 高临界电流密度的铌三锡超导股线的制备方法
CN115295243B (zh) * 2022-09-30 2022-12-30 西部超导材料科技股份有限公司 元素掺杂型高临界电流密度的铌三锡超导股线的制备方法

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US20170062099A1 (en) 2017-03-02
WO2015175064A3 (fr) 2016-01-07
US9916919B2 (en) 2018-03-13
CN106170464B (zh) 2020-07-28
CN106170464A (zh) 2016-11-30
EP3107879A4 (fr) 2017-11-15
EP3107879A2 (fr) 2016-12-28
US20180158577A1 (en) 2018-06-07

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